WO2015055510A1 - NdBR WITH MOLAR MASS BREAKDOWN - Google Patents

NdBR WITH MOLAR MASS BREAKDOWN Download PDF

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Publication number
WO2015055510A1
WO2015055510A1 PCT/EP2014/071684 EP2014071684W WO2015055510A1 WO 2015055510 A1 WO2015055510 A1 WO 2015055510A1 EP 2014071684 W EP2014071684 W EP 2014071684W WO 2015055510 A1 WO2015055510 A1 WO 2015055510A1
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WIPO (PCT)
Prior art keywords
polymer
neodymium
process according
ndbr
molar mass
Prior art date
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PCT/EP2014/071684
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English (en)
French (fr)
Inventor
Heike Kloppenburg
Alicia Le-Sattler
Original Assignee
Lanxess Deutschland Gmbh
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Filing date
Publication date
Priority to JP2016524484A priority Critical patent/JP6363705B2/ja
Priority to MX2016004886A priority patent/MX2016004886A/es
Priority to CN201480056261.3A priority patent/CN105764928A/zh
Priority to EP14781603.7A priority patent/EP3057998B1/en
Priority to SG11201602765QA priority patent/SG11201602765QA/en
Priority to KR1020217019363A priority patent/KR102304489B1/ko
Priority to US15/029,029 priority patent/US20160257770A1/en
Priority to KR1020167012765A priority patent/KR102270433B1/ko
Application filed by Lanxess Deutschland Gmbh filed Critical Lanxess Deutschland Gmbh
Priority to RU2016118594A priority patent/RU2660853C2/ru
Priority to BR112016008352-0A priority patent/BR112016008352B1/pt
Publication of WO2015055510A1 publication Critical patent/WO2015055510A1/en
Priority to SA516370934A priority patent/SA516370934B1/ar
Priority to ZA2016/03258A priority patent/ZA201603258B/en
Priority to US15/457,074 priority patent/US9963519B2/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
    • C08C19/00—Chemical modification of rubber
    • C08C19/20—Incorporating sulfur atoms into the molecule
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
    • C08C19/00—Chemical modification of rubber
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
    • C08C19/00—Chemical modification of rubber
    • C08C19/08—Depolymerisation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F136/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F136/02—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
    • C08F136/04—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
    • C08F136/06—Butadiene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
    • C08K5/3415—Five-membered rings
    • C08K5/3417—Five-membered rings condensed with carbocyclic rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/37—Thiols
    • C08K5/372—Sulfides, e.g. R-(S)x-R'
    • C08K5/3725—Sulfides, e.g. R-(S)x-R' containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L15/00—Compositions of rubber derivatives

Definitions

  • the invention relates to neodymium-catalysed polybutadienes (NdBR) comprising > 95 wt% of cis-1 ,4 units and ⁇ 1 wt% of 1 ,2-vinyl content, based on the neodymium- catalysed polybutadiene, a process for production thereof, a rubber mixture comprising such NdBR and uses thereof.
  • NdBR neodymium-catalysed polybutadienes
  • Polybutadienes are used as important constituents of rubber mixtures in the tyre industry in order to achieve an improvement in final properties, for instance a reduction in rolling resistance and in abrasion value.
  • a further field of use is in golf-ball cores or shoe soles, the primary concern in this case being a high rebound resilience.
  • polybutadienes having a high fraction of cis-1 ,4 units have been manufactured on a large industrial scale and used for the production of tyres and other rubber products and also for impact modification of polystyrene.
  • neodymium-catalysed polybutadienes within the group of high-cis polybutadienes have particularly advantageous properties with regard to rolling resistance, abrasion value and rebound resilience.
  • the catalyst systems used play an important part in the production of polybutadienes.
  • the industrially employed neodymium catalyst for example, is a Ziegler-Natta system, which is formed from a plurality of catalyst components. Catalyst formation involves the formation of mostly different catalytic sites, resulting in an at least bimodal molar mass distribution in the polymer.
  • the familiar three catalyst components usually being a neodymium source, a chloride source and an organoaluminium compound, are mixed in various ways under defined temperature conditions to ready the catalyst system, with or without ageing, for the polymerization.
  • the prior art discloses several processes for preparing Ziegler-Natta catalyst systems used in the production of polybutadienes.
  • EP 0 127 236 wherein the catalyst is prepared by mixing neodymium oxides, neodymium alkoxides and carboxylates with an organometallic halide and also with an organic compound at a temperature of 20°C to 25°C.
  • the mixing temperature for these four components may also be in the range from 50°C to 80°C.
  • the mixture is cooled down to a temperature in the range from 20 to 25°C, at which point diisobutylaluminium hydride (DIBAH) is added. There is no mention of any ageing.
  • DIBAH diisobutylaluminium hydride
  • EP 1 176 157 B1 discloses a process for production of polybutadienes having a reduced ratio for solution viscosity/Mooney viscosity, wherein catalyst preparation is carried out with pre-forming. First the neodymium versatate is mixed with DIBAH and isoprene at 50°C, then this mixture is cooled down to 5°C, thereafter ethylaluminium sesquichloride (EASC) is admixed. Ageing can take from several minutes to several days at a temperature between 10°C and -80°C.
  • EASC ethylaluminium sesquichloride
  • Comonomers a bisdiene for example, are added during polymerization to enhance the branching of the polymers and thus also to obtain the very narrow ratio of solution viscosity/Mooney viscosity.
  • the branched polymer obtained in the process has at least four free chain ends per molecule due to the coupling via the bisdiene, whereas linear molecules have just two chain ends.
  • the number of chain ends in a polymer has a direct correlation with energy dissipation performance.
  • the energy dissipation performance of a polymer increases with the number of free chain ends.
  • the lower the energy dissipation performance of a polymer the lower, for example, the rolling resistance and the better the rebound resilience of the polymer.
  • the final properties of a linear polymer having just two chain ends per molecule will always be better than those of a branched polymer.
  • step increase in Mooney viscosity and similar expressions such as “step increase in Mooney value", “Mooney jumped” or “Mooney jump” refer to techniques to further enhance the Mooney viscosity of polymers after their polymerization.
  • Raising the molecular weight of elastomeric unsaturated diene polymers is important for various reasons. It first of all makes it possible to produce low molecular weight parent polymers, which has the immense advantage in relation to the solution polymerization techniques typically employed of entailing lower viscosities in the "cement" (the solution of the polymer in the organic solvent medium used in the polymerization) and of permitting operation where there is a higher solids content in the "cement", since superior heat transfer is achieved. It is further possible to reduce the cold flow of such diene polymers, thus increasing their capability for oil-extension.
  • pre-forming can change the catalytic effect of Nd catalysts.
  • Such preformed Nd catalysts deliver polymers having relatively low cold flow, however, pre-forming usually reduces catalyst activity, so in some instances there is a considerable increase in neodymium consumption.
  • polydienes having low cold flow are obtainable by treating the diene polymers with disulphur dichloride, sulphur dichloride, thionyl chloride, disulphur dibromide or thionyl bromide after the polymerization (DE-B 12 60 794).
  • DE-B 12 60 794 the process for producing elastomeric diene polymers which is described in DE-B 12 60 794 is disadvantageous in that this process is unsuitable for high molecular weight neodymium-catalysed polybutadiene when the Mooney jump is to be not less than 50% higher than the Mooney viscosity of the polymer after the polymerization.
  • the problem addressed by the present invention is therefore that of providing high molecular weight neodymium-catalysed polybutadienes (NdBR) capable of delivering vulcanizates having good dynamic final properties for polymers of high molar mass and Mooney viscosity, low rolling resistance, good crack resistance and low abrasion values coupled with good processing properties, for instance a shortened mixing time, versus unmodified NdBRs of the same Mooney viscosity, and a simplified extrudability at an increased strand speed.
  • NdBR neodymium-catalysed polybutadienes
  • the invention provides neodymium-catalysed polybutadienes (NdBR) comprising > 95 wt% of cis-1 ,4 units and ⁇ 1 wt% of 1 ,2-vinyl content, based on the neodymium- catalysed polybutadiene, which evince a molar mass breakdown of not less than 25%.
  • NdBR neodymium-catalysed polybutadienes
  • the molar mass breakdown is effected by mixing a masticating agent with the NdBR, measuring the Mooney viscosity (ML 1 +4 at 100°C) of the NdBR before and after the mixing with the masticating agent and determining by calculation the percent change between the Mooney viscosities.
  • the NdBR of the invention evinces a molar mass breakdown of not less than 33%, more preferably not less than 50%.
  • K Mooney viscosity (ML 1 +4 at 100°C) of NdBR before mixing with masticating agent and, in the case where the polymer is Mooney jump modified, then such Mooney viscosity (ML 1 +4 at 100°C) being subsequent to the modification, and
  • L Mooney viscosity (ML 1 +4 at 100°C) of NdBR after mixing with masticating agent.
  • molar mass breakdown is of particular importance in the case of natural rubbers. Since natural rubber is difficult to process because of its high molar mass and gel content, processing is usually preceded by an operation known as mastication to intentionally bring about polymer chain cleavage. This breakdown of polymer chains may be effected either mechanically or thermal-oxidatively. The mechanical breakdown of natural rubbers is brought about on roll mills at high friction. The thermal-oxidative breakdown utilizes a series of substances (masticating agents, peptizers) to catalyse the oxidative process of breakdown. 2,2'-Dibenzamidodiphenyl disulphide (DBD) is an efficacious breakdown accelerant, while organic complexes of metal activate the process.
  • DBD 2,2'-Dibenzamidodiphenyl disulphide
  • the masticating agent comprises a mixture containing iron phthalocyanine and 2,2'- dibenzamidodiphenyl disulphide, waxes and fillers.
  • the masticating agent is mixed with the solid NdBR material. Any customary mixing assembly can be used for this, for example rolls, kneaders, mixers or extruders. On a roll is where mixing is typically carried out. Any roll may be selected.
  • the ideal choice for analytical proof of concept is a laboratory roll, which is preferably capable of handling polymers from 100 g to 2 kg.
  • Roll diameter is preferably between 5 and 30 cm.
  • Roll nip is chosen such that the milled sheet produced will be homogeneous.
  • Roll nip is preferably between 0.3 and 2 mm, more preferably between 0.4 and 1 mm.
  • Roll speed is chosen such that the operator can work efficiently and the milled sheet can be cut and folded over by hand to improve homogenization.
  • the roll may be operated with or without friction.
  • the amount of masticating mixture used may be between 0.1 and 2 wt% based on the polymer used. Larger amounts of masticating agent may also be added, but this will not result in any further increase in efficacy, while an excess of masticating mixture may further reduce the Mooney viscosity after the treatment.
  • the roll may be heated by an external temperature-regulating system to different temperatures. Temperatures between 70°C and 160°C are preferable and between 80°C and 120°C are particularly preferable.
  • the ideal roll temperature is easily determined by preliminary tests. It depends on the heat transfer from the roll to the polymer, which in turn depends on the ratio of the roll surface area to the amount of polymer used, and on the activator used.
  • Roll temperature is preferably between 90°C and 120°C when iron phthalocyanine, as an activator, is used. Without activator in the masticating mixture, higher temperatures are preferably needed, and they are typically between 100°C and 140°C.
  • Treatment duration depends on the temperature of the polymer on the roll and on the activator used in the masticating mixture. Treatment time is typically between 1 min and 30 min and may be determined by preliminary tests. An optimum combination of roll temperature and polymer quantity and amount of masticating mixture can ideally reduce the treatment time to the range from 1 to 10 min.
  • the invention further provides a process for producing the neodymium-catalysed polybutadienes (NdBR) of the present invention, wherein
  • butadiene monomer is polymerized in the presence of at least one inert organic solvent and in the presence of at least one catalyst based on neodymium compounds at temperatures of 60°C to 140°C,
  • the temperature in step 3) is preferably in the range from 66°C to 140°C, more preferably at 75°C - 100°C.
  • the modifying treatment takes less than 15 minutes, preferably 10 minutes.
  • Step 3) is preferably carried out with a static mixer or dynamic mixer.
  • this process surprisingly produced the high molecular weight neodymium- catalysed polybutadiene (NdBR) of the present invention, which evinces a molar mass breakdown with a masticating agent by not less than 25%, based on the Mooney viscosity (ML 1 +4 at 100°C), while the molar mass breakdown is effected by mixing a masticating agent with the NdBR, measuring the Mooney viscosity (ML 1 +4 at 100°C) of the NdBR before and after the mixing with the masticating agent and determining the molar mass breakdown arithmetically.
  • NdBR neodymium- catalysed polybutadiene
  • the conversion of the sulphur chlorides is preferably not less than > 90%, more preferably not less than > 95% and even more preferably > 97%.
  • the pH of the polymer solution according to the present invention is ideally in the range from 6 to 7 in that the conversion would then be > 97%.
  • the higher the sulphur chloride conversion the gentler the process is on the plant equipment. This is because the subsequent stripping process may liberate HCI, which may lead to corrosion of plant equipment.
  • the process of the present invention thus reduces and/or entirely prevents plant corrosion due to evolved HCI.
  • the polymer solution from the polymerization is stirred with water, the amount of water used being equal to the amount of polymer solution.
  • the water used has a pH of 7.
  • the pH of the water is again measured after a few minutes, typically after 5 to 10 min.
  • the water is titrated against NaOH. The end point may be determined not only visually against an indicator but also with a pH electrode.
  • the gel content of the polybutadiene produced according to the process of the present invention is preferably less than 1 wt%, more preferably less than 0.3 wt% and even more preferably less than 0.2 wt%.
  • the method of determining the gel content is described hereinbelow.
  • Jumped polymer high molecular weight polybutadiene after modification, after the Mooney jump or after the jump reaction. It is preferable to use Ziegler-Natta catalysts based on compounds of the rare earth metals, such as cerium, lanthanum, praseodymium, gadolinium or neodymium compounds, that are soluble in hydrocarbons.
  • the rare earth metals such as cerium, lanthanum, praseodymium, gadolinium or neodymium compounds, that are soluble in hydrocarbons.
  • the Ziegler- Natta catalysts used to be the corresponding salts of the rare earth metals such as neodymium carboxylates, in particular neodymium neodecanoate, neodymium octanoate, neodymium naphthenate, neodymium 2,2-diethylhexanoate or neodymium 2,2-diethyl- heptanoate, such as neodymium phosphates, in particular neodymium tris(2-ethylhexyl phosphate)s, as described in WO-200238636 for example, and also the corresponding salts of lanthanum or of praseodymium.
  • Useful Ziegler-Natta catalysts further comprise catalyst systems based on metallocenes, as described in EP-A 1025136 and EP-A 1078939 for example.
  • the process of the present invention is preferably carried out using the following steps: a) polymerizing butadiene monomer in the presence of at least one inert organic solvent and in the presence of at least one catalyst based on neodymium compounds at temperatures of 60°C to 140°C, in a preferred embodiment, there is the catalyst preparation with or without preforming by using catalyst systems based on neodymium comprising component A: an alkoxide, a phosphate or a carboxylate of neodymium, preferably neodymium versatate, component B: an alkylaluminium compound, preferably diisobutylaluminium hydride (DIBAH), component C: a diene, preferably butadiene, and component D: at least one halogen compound, preferably ethylaluminium sesquichloride (EASC), b) stopping the polymerization with reactive compounds, thereby forming a first polymer, c) admixing sulphur
  • the process may also comprise the further steps of: c1 ) after step c) prior to step d) measuring the Mooney viscosity of the Mooney jumped polymer, e) after step d) again measuring the Mooney viscosity of the polymer, and f) calculating the molar mass breakdown % of the polymer.
  • steps d), e) and f) may be repeated as necessary to achieve a desired molar mass breakdown %.
  • Useful dienes include butadiene, isoprene, pentadiene and 2,3-dimethylbutadiene, especially butadiene and isoprene.
  • the recited dienes may be used not only individually but also mixed with one another, producing either homopolymers or copolymers of the recited dienes.
  • organic solvents These solvents have to be inert to the catalyst system used.
  • Suitable solvents include, for example, aromatic, aliphatic and cycloaliphatic hydrocarbons such as benzene, toluene, pentane, n-hexane, isohexane, heptane, isomeric pentanes, cyclohexane, methylcyclopentane and cyclohexane. These solvents may be used individually or in combination. Cyclohexane and n-hexane are preferable. Blending with polar solvents is likewise possible.
  • the inert organic solvents are used in amounts of 200 to 900 parts by weight, based on 100 parts by weight of monomers. Amounts of 300 to 500 parts by weight are preferable.
  • the polymerization may be carried out not only continuously but also batchwise.
  • the polymerization is carried out at a temperature in the range from 60° to 140°C.
  • the polymerization may be carried out in a conventional manner in one or more stages, in batch operation or in continuous operation. Preference is given to a continuous operation in a reactor cascade consisting of a plurality of reactors, preferably at least 2, in particular from 2 to 6.
  • the catalyst is deactivated in a conventional manner by addition of reactive compounds, such as protic compounds, i.e. the polymerization is stopped.
  • the amount of protic compounds is preferably from 0 to 1 phr based on the monomer used.
  • Reactive compounds preferably comprise fatty acids, in which case saturated, monounsaturated or polyunsaturated vegetable or animal fatty acids, such as lauric acid, myristic acid, palmitic acid, oleic acid or versatic acid, can be used.
  • carboxylic acid may preferably not be necessary. It is further possible on attainment of the desired conversion to react the catalyst with one or more reactive polar organic compounds which, following the reaction with the catalyst, may form a functional end group attached to the polymer chain.
  • the sulphur chlorides preferably comprise disulphur dichloride, sulphur dichloride and/or thionyl chloride or any mixture thereof.
  • sulphur halides in which case chlorine or bromine is used as halogen, chlorine being used with preference.
  • Dihalides of sulphur are customary, while the sulphur content per molecule may be in the range from 1 to 8 sulphur atoms, and preferably there are two sulphur atoms per halide. It is particularly preferable to effect the modification with disulphur dichloride.
  • the amount of sulphur chlorides, preferably disulphur dichloride, admixed per 100 parts by weight of diene rubber is generally in the range from 0.05 to 0.7 part by weight and preferably in the range from 0.1 to 0.4 part by weight.
  • Modifying is typically effected at temperatures of 66°C to 140°C, preferably at 75°C to 100°C, while modification takes less than 15 minutes, preferably 10 minutes.
  • Customary stabilizer may be added in customary amounts to the polymer solution prior to work-up.
  • Useful stabilizers include, for example, sterically hindered phenols, e.g. 2,6-di- tert-butyl-4,5-methylphenol, 4,6-bis(octylthiomethyl)-o-cresol or octadecyl 3-(3,5-di-tert- butyl-4-hydroxyphenyl)propionate or aromatic amines, such as N-(1 ,3-dimethylbutyl)-N'- phenyl-para-phenylenediamine or phosphites, e.g. tris(nonylphenyl) phosphite.
  • Other commercially available stabilizers may also be used.
  • the polymers are isolated by evaporating the polymer solution, by precipitating with a nonsolvent such as, for example, methanol, ethanol, acetone, or preferably by steam distilling the solvent.
  • a nonsolvent such as, for example, methanol, ethanol, acetone, or preferably by steam distilling the solvent.
  • Drying is carried out in a conventional manner, for example in a drying cabinet or in a screw dryer.
  • the high molecular weight neodymium-catalysed polybutadiene (NdBR) thus obtained comprises > 90 wt% of cis-1 ,4 units and ⁇ 1 wt% of 1 ,2-vinyl butadiene content, based on the neodymium-catalysed polybutadiene, evinces a molar mass breakdown of not less than 25%, based on the Mooney viscosity (ML 1 +4 at 100°C), while the molar mass breakdown is effected by mixing a masticating agent with the NdBR, measuring the Mooney viscosity (ML 1 +4 at 100°C) of the NdBR before and after the mixing with a masticating agent.
  • the high molecular weight polybutadiene (NdBR) of the present invention preferably evinces significantly reduced gelling, if any.
  • the gel content is preferably less than 1 wt%.
  • the NdBR of the present invention preferably has the following properties:
  • the neodymium-catalysed polybutadiene of the present invention does not require any additions of extender oils, as of aromatic extender oils for example, to adjust the Mooney viscosity of the rubbers.
  • the polybutadienes of the present invention may be used alone, cut with aromatic or aliphatic oils or mixed with other rubbers.
  • Additional rubbers suitable for producing rubber vulcanizates include not only natural rubber but also synthetic rubbers. They include
  • SBR - styrene-butadiene copolymers having styrene contents of 1 to 60, preferably 20 to 50 wt%
  • NBR - butadiene-acrylonitrile copolymers having acrylonitrile contents of 5 to
  • EPDM - ethylene-propylene-diene monomer copolymers and also mixtures thereof are, in particular, natural rubber, emulsion SBR and also solution SBR rubbers with a glass transition temperature above -50°C, optionally modified with silyl ethers or with other functional groups, as described in EP-A-0 447 066, polybutadiene rubber having high 1 ,4-cis content (> 90 wt%) produced with Ni-, Co-, Ti- or Nd-based catalysts, and also polybutadiene rubber having a vinyl content of 0 to 75 wt% and also mixtures thereof.
  • the rubber mixtures represent a further part of the subject-matter of the invention and generally contain from 5 to 300 parts by weight of an active or inert filler, e.g. finely divided silicas as obtained for example by precipitation of solutions of silicates or flame hydrolysis of silicon halides with specific surface areas of 5 to 1000, preferably 20 to 400 m 2 /g (BET surface area) and with primary particle sizes of 10 to 400 nm.
  • an active or inert filler e.g. finely divided silicas as obtained for example by precipitation of solutions of silicates or flame hydrolysis of silicon halides with specific surface areas of 5 to 1000, preferably 20 to 400 m 2 /g (BET surface area) and with primary particle sizes of 10 to 400 nm.
  • the silicas may optionally also be present as mixed oxides with other metal oxides, such as the oxides of Al, of Mg, of Ca, of Ba, of Zn, of Zr or of Ti, synthetic silicates, such as aluminium silicate, alkaline earth metal silicate such as magnesium silicate or calcium silicate, with BET surface areas of 20 to 400 m 2 /g and primary particle diameters of 10 to 400 nm, natural silicates, such as kaolin and other naturally occurring silica, glass fibres and glass fibre products (mats, strands) or glass microbeads, metal oxides, such as zinc oxide, calcium oxide, magnesium oxide, aluminium oxide, metal carbonates, such as magnesium carbonate, calcium carbonate, zinc carbonate, metal hydroxides, e.g.
  • other metal oxides such as the oxides of Al, of Mg, of Ca, of Ba, of Zn, of Zr or of Ti
  • synthetic silicates such as aluminium silicate, alkaline earth metal silicate such as magnesium silicate or
  • the carbon blacks to be used here are produced by the lamp-black process, the furnace-black process or the gas-black process and have BET surface areas of 20 to 200 m 2 /g, e.g. SAF, ISAF, HAF, FEF or GPF blacks.
  • rubber gels in particular those based on polybutadiene, butadiene-styrene copolymers, butadiene-acrylonitrile copolymers and polychloroprene.
  • Zinc diacrylates, finely divided silicas and carbon blacks are particularly preferable.
  • the recited fillers can be used alone or mixed.
  • the rubber mixtures contain by way of fillers a mixture of light-coloured fillers, such as finely divided silicas, and carbon blacks, wherein the mixing ratio of light-coloured fillers to carbon blacks is in the range from 0.05 to 20, preferably in the range from 0.1 to 10.
  • the form in which the fillers are added to the solution of the polybutadiene(s) of the present invention is preferably that of solids or of a slurry in water or a solvent.
  • the rubber solution may be prepared beforehand, but preferably the as-polymerized solution is used directly.
  • the solvent is subsequently removed thermally or preferably with the aid of steam. The conditions for this stripping operation are easily determined by preliminary tests.
  • the fillers are further preferably admixed to the solid polybutadiene of the invention or to a mixture of rubbers and incorporated in a known manner, for example by using a kneader.
  • the rubber mixtures of the present invention may optionally further comprise crosslinkers.
  • Crosslinkers used may be sulphur or peroxides, in which case sulphur is particularly preferred.
  • the rubber mixtures of the present invention may contain further rubber auxiliaries, such as reaction accelerators, antioxidants, heat stabilizers, light stabilizers, antiozonants, processing aids, plasticizers, tackifiers, blowing agents, dyes, pigments, waxes, extenders, organic acids, retarders, metal oxides and also activators such as triethanolamine, polyethylene glycol, hexanetriol, etc., that are known to the rubber industry.
  • Preferred filler activators include sulphur-containing silyl ethers, in particular bis(trialkoxysilylalkyl) polysulphides, as described in DE-A-2 141 159 and DE-A-2 255 577, oligomeric and/or polymeric sulphur- containing silyl ethers of DE-A-4 435 31 1 and EP-A-0 670 347, mercapto- alkyltrialkoxysilanes, in particular mercaptopropyltriethoxysilane and thiocyanatoalkyl silyl ethers, as described in DE-A-195 44 469 for example.
  • the rubber auxiliaries are used in customary amounts, which depend inter alia on the intended use.
  • customary amounts are amounts from 0.1 to 50 wt%, based on rubber.
  • the further blending of the rubbers with the other rubber auxiliaries, crosslinkers and accelerators mentioned may be carried out in a conventional manner with the aid of suitable mixing assemblies, such as rolls, internal mixers and mixing extruders.
  • suitable mixing assemblies such as rolls, internal mixers and mixing extruders.
  • the rubber mixtures of the present invention may be vulcanized at customary temperatures of 100 to 200°C, preferably 130 to 180°C (optionally under a pressure of 10 to 200 bar).
  • the rubber mixtures of the present invention are very useful for producing shaped articles of any kind.
  • Nonlimiting examples of these shaped articles are O-rings, profiles, gaskets, membranes, tyres, tyre treads, damping elements and hoses.
  • the rubber mixtures of the present invention are further useful for impact modification of thermoplastics, in particular for polystyrene and styrene-acrylonitrile copolymers.
  • the use of the rubber mixtures for golf balls, in particular golf-ball cores, is particularly apt.
  • NdBR neodymium-catalysed polybutadienes
  • Comparative Example 1 conventional NdBR with Mooney jump, admixture of S 2 CI 2 1 a) Polymerization: A dry, nitrogen-inertized 20 L steel autoclave was charged with 8500 g of hexane (dried over molecular sieve), 1300 g of 1 ,3-butadiene, 21 mmol of a 20% solution of diisobutylaluminium hydride in hexane, 1 .44 mmol of a 10% solution of ethylaluminium sesquichloride in hexane, and also 1 .44 mmol of a 40% solution of neodymium versatate in hexane. The autoclave contents were heated to 73°C with stirring and polymerized for 60 min with stirring. The temperature in the reactor rose to 90°C. Butadiene conversion after the polymerization was 98.7%.
  • the polymerization was stopped by admixture of 6.5 g of stearic acid (0.5 phr). The solution was kept at 90°C for a further 15 min.
  • the NdBR was precipitated from the remaining solution by passing this remainder into 5 kg of ethanol, stabilized with Irganox 1520 (0.2 phr) and vacuum dried at 70°C.
  • Masticating agent 4 g of DBD were mixed with 6 g of talcum and 0.08 g of iron phthalocyanine in a mortar.
  • a dry, nitrogen-inertized 20 L steel autoclave was charged with 8500 g of hexane (dried over molecular sieve), 1300 g of 1 ,3-butadiene, 21 mmol of a 20% solution of diisobutylaluminium hydride in hexane, 1.44 mmol of a 10% solution of ethylaluminium sesquichloride in hexane, and also 1 .44 mmol of a 40% solution of neodymium versatate in hexane.
  • the autoclave contents were heated to 73°C with stirring and polymerized for 60 min with stirring. The temperature in the reactor rose to 90°C.
  • the polymerization was stopped by admixture of 6.5 g of stearic acid (0.5 phr). A conversion test sample was taken. Butadiene conversion after the polymerization was found to be 98.7%.
  • the NdBR was precipitated from the remaining solution by passing this remainder into 5 kg of ethanol, stabilized with Irganox 1520 (0.2 phr) and vacuum dried at 70°C. Final weight after drying: 1263 g.
  • Masticating agent 4 g of DBD were mixed with 6 g of talcum and 0.08 g of iron phthalocyanine in a mortar.
  • the polymer solution was admixed with 3.33 g of disulphur dichloride (0.3 phr) at 95°C for modification. The solution was stirred at 95°C for a further 10 min. A 100 g sample was taken of the solution for pH determination.
  • the NdBR was precipitated from the remaining solution by passing this remainder into 5 kg of ethanol, stabilized with Irganox 1520 (0.2 phr) and vacuum dried at 70°C.
  • A Determination of gel content of polybutadiene in styrene by gravimetric methods similar to the BAYELAS MO AQ 259 - A LAB method: 25.0 g of polymer are weighed out on a laboratory balance to an accuracy of 0.1 g. The edges were previously cut off and discarded. The polymer is cut into small pieces. A 1 I wide-neck bottle is initially charged with 850 ml of filtered styrene and the polymer is dissolved on a shaker in the course of about 4 hours.
  • a wire gauze consisting of a woven wire cloth having a mesh size of 0.036 mm, 0 50 mm, is heated to red heat and placed in a desiccator bottle to cool down. After cooling, the wire gauze is moved from the desiccator bottle and weighed on an analytical balance to an accuracy of 0.1 mg. This is weight A. Three glass beakers are provided which each contain 100 ml of filtered styrene. The wire gauze with a diameter of 50 mm is placed in the "Gelman" metal filtration system (seal-filter-seal), and the funnel attachment is screwed into place.
  • the polymer solution is then poured through the filter.
  • the first of the three styrene- containing glass beakers is used to rinse the wide-neck bottle, and this solution is likewise passed through the filter.
  • the filter is subsequently rinsed with the other two styrene portions.
  • the filter is then carefully removed with pincers and placed on a clean paper tissue. Pressure is carefully applied with the pincers to the edge of the filter.
  • An eyeglass is used to observe the evaporating styrene.
  • the moist wire filter, still wetted with styrene becomes visibly lighter in colour as the amount of styrene decreases. Once all the filter meshes are free from styrene, the filter is immediately weighed back on the balance. This is weight B.
  • the filter After the second weighing of the filter, the filter is dried in a drying cabinet at 100°C ( ⁇ 5°C) for 15 minutes in order to determine the dry gel content. All the while the filter is situated in an open desiccator bottle. After drying, the bottle plus filter is placed in the desiccator for about 10 minutes to cool down and then reweighed. This is weight C.
  • a Brookfield DV-I rotary viscometer is used to measure a 5.43% polymer solution in toluene at room temperature.
  • ELA 101 A solution of the polymer in toluene is poured on a KBr window, the solvent is evaporated and the polymer film is measured by FTIR spectroscopy between 2 KBr windows.
  • Irganox 1520 4,6-bis(octylthiomethyl)-o-cresol from BASF
  • deionized water having a pH of 7 (at 25°C) is used.
  • 100 g of the polymer solution from the polymerization are removed and stirred up with 100 g of water in a glass vessel equipped with a KPG stirrer.
  • the temperature is 50°C and is set via an external water bath. Stirring time is 10 min.
  • the pH of the aqueous phase is measured.
  • F amount of water used / amount of titrated water, where the amount of extracted polymer solution corresponds to the amount of water used for extraction.
  • Rubber mixtures were produced to contain BUNATM CB 24 as Nd-catalysed polybutadienes without modification (P1 ), the polymer of Example 3b) with Mooney jump, but without modification (P2) and the inventive polymer 4c) from Example 2 after molar mass breakdown (P3).
  • P1 * , P2 * and P3 * 50 phr of the particular abovementioned polybutadienes were admixed with 50 phr of natural rubber in each case.
  • the mixture constituents are listed in Table 1 .
  • the mixtures were first produced in a 1 .5 L kneader without sulphur and accelerator.
  • the mixture constituents sulphur and accelerator were then admixed on a roll at 40°C.
  • Table 2 shows the recipes and the measured test results.
  • VIVATEC 500 as oil Hansen und Rosenthal KG
  • RHENOGRAN IS 60-75 as sulphur RheinChemie Rheinau GmbH
  • Inventive vulcanizates P3 and P3 * versus comparative examples P1 and P2 and also P1 * and P2 * exhibit a reduction in the vulcanization time needed in Monsanto MDR: an improvement in the indicators for low rolling resistance, such as high rebound resilience at 60°C, a low tangent delta maximum in the MTS test at 60°C and a low tangent delta at 60°C in the Epiexor test, also superior results in the stress-strain test, as evident from a higher quotient from S300/S10 and also in the case of the mixture with natural rubber P3 * versus P1 * and P2 * very low values in the abrasion test.
  • DIN53513 dynamic damping via Eplexor equipment - Eplexor equipment (Eplexor 500 N) from Gabo-Testanlagen GmbH, Ahlden, Germany was used to determine dynamic properties (temperature dependency of storage modulus E' in the temperature range from -60°C to 0°C and also tan ⁇ at 60°C). The values were determined in accordance with DIN53513 at 10 Hz on Ares strips in the temperature range from -100°C to +100°C at a heating rate of 1 K/min. The method was used to obtain the following variables, the terminology here being in accordance with ASTM 5992-96:
  • E' provides an indication of the grip of a winter tyre tread on ice and snow. As E' decreases, grip improves.
  • tan ⁇ (60°C) is a measure of hysteresis loss from the tyre under operating conditions. As tan ⁇ (60°C) decreases, the rolling resistance of the tyre decreases.
  • DIN53513-1990 Elastic properties - An MTS elastomer test system (MTS Flex Test) from MTS was used to determine the elastic properties.
  • the measurements were carried out in accordance with DIN53513-1990 on cylindrical samples (2 samples each 20 x 6 mm) with a total 2 mm compression at a temperature of 60°C and a measurement frequency of 1 Hz in the range of amplitude sweep from 0.1 to 40%.
  • G * (0.5%) - (15%): difference of dynamic modulus at 0.5% relative to 15% amplitude sweep and also tan ⁇ (max): maximum loss factor (G'VG') of entire measuring range at 60°C.
  • G * (0.5%) - (15%) is an indication of the Payne effect of the mixture in that a low value indicates good filler distribution and hence a low rolling resistance.
  • tan ⁇ (max) is a measure of the hysteresis loss from the tyre under operating conditions. As tan ⁇ (max) decreases, the rolling resistance of the tyre decreases.

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  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
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US15/029,029 US20160257770A1 (en) 2013-10-16 2014-10-09 NdBR WITH MOLAR MASS BREAKDOWN
CN201480056261.3A CN105764928A (zh) 2013-10-16 2014-10-09 具有摩尔质量断裂的NdBR
EP14781603.7A EP3057998B1 (en) 2013-10-16 2014-10-09 Ndbr with molar mass breakdown
SG11201602765QA SG11201602765QA (en) 2013-10-16 2014-10-09 NdBR WITH MOLAR MASS BREAKDOWN
KR1020217019363A KR102304489B1 (ko) 2013-10-16 2014-10-09 몰 질량 감소를 가지는 NdBR
JP2016524484A JP6363705B2 (ja) 2013-10-16 2014-10-09 モル質量が分断されたＮｄＢＲ
KR1020167012765A KR102270433B1 (ko) 2013-10-16 2014-10-09 몰 질량 감소를 가지는 NdBR
MX2016004886A MX2016004886A (es) 2013-10-16 2014-10-09 Ndbr con degradacion de la masa molar.
RU2016118594A RU2660853C2 (ru) 2013-10-16 2014-10-09 NdBR С ПАДЕНИЕМ МОЛЯРНОЙ МАССЫ
BR112016008352-0A BR112016008352B1 (pt) 2013-10-16 2014-10-09 Processo para a produção de polibutadienos catalisados com neodímio (ndbr), composição de borracha que contêm um polibutadieno catalisado com neodímio (ndbr) e uso de composição de borracha
SA516370934A SA516370934B1 (ar) 2013-10-16 2016-04-13 بولي بيوتاديين محفزة بنيوديميوم مع انخفاض الكتلة المولارية
ZA2016/03258A ZA201603258B (en) 2013-10-16 2016-05-13 Ndbr with molar mass breakdown
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KR102173756B1 (ko) 2017-10-18 2020-11-04 주식회사 엘지화학 변성 공액디엔계 중합체의 제조방법
CN109553803A (zh) * 2018-12-17 2019-04-02 山东阳谷华泰化工股份有限公司 一种环保型颗粒状塑解剂及其制备方法
KR102342259B1 (ko) * 2018-12-21 2021-12-24 주식회사 엘지화학 변성 공액디엔계 중합체 및 이를 포함하는 고무 조성물
CN113166315B (zh) * 2018-12-21 2023-08-01 株式会社Lg化学 改性共轭二烯类聚合物的制备方法
KR102666895B1 (ko) * 2019-11-21 2024-05-20 주식회사 엘지화학 변성 공액디엔계 중합체의 제조방법
US20230303734A1 (en) 2020-09-28 2023-09-28 Arlanxeo Deutschland Gmbh Partially hydrogenated diene polymers
CN118696068A (zh) 2022-04-08 2024-09-24 阿朗新科德国有限责任公司 支化的改性二烯橡胶

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